4-naphthalimido cycloammonium-acrylic fiber compositions

ABSTRACT

Acrylic fibre-bleaching cation composition of matter in which the cation has the formula: IN WHICH R is an alkyl radical or a hydroxy or alkoxy substituted alkyl radical, said alkyl having one to four carbon atoms, X is a direct linkage or p-phenylene, B is an N - (lower alkyl) cycloammonium group attached to X through a carbon atom, the remaining carbon atoms in B being unsubstituted or substituted by chlorine, lower alkyl, phenyl or methylthio group.

llnited States Patent '1191 Mingasson et a1.

1 1 4-NAPHTHALIMIDO CYCLOAMMONIUM-ACRYLIC FIBER COMPOSITIONS [75] Inventors: Georges Raymond Henry Mingasson, Paris; Annick Marthe 1 Suzanne Simone Domergue, Eaubonne, both of France [73] Assignee: Ugine Kuhlmann, Paris, France [22] Filed: Dec. 1, 197] [21] Appl. No.: 203,918

Related U.S. Application Data [62] Division of Ser. No. 751,349, Aug. 9, 1968, Pat. No.

[30] Foreign Application Priority Data Aug. 11, 1967 France 67.117728 52 us. or 252/3012 w, 8/1 w, s/177, 260/281 [51] Int. Cl C09k l/02 [58] Field of Search 260/281, 88.7 B; 8/177; 252/301.2 W

[56] References Cited UNITED STATES PATENTS 3,247,208 4/1966 Schenker 260/281 3,310,564 3/1967 Kasai 260/281 3,330,834 7/1967 Sensitu et a1. 260/281 3,624,080 11/1971 Dimroth 260/281 X 3,625,947 12/1971 Nogouchi 260/281 3,649,633 3/1972 Mingasson et a1. 260/281 3,697,525 10/1972 Okada et a1. 260/281 Nov. 19, 1974 3,798,224 3/1974 Hirakata et a1. 260/281 3,804,837 4/1974 Mingasson 3,804,838 4/1974 Mingasson .1 260/270 FOREIGN PATENTS OR APPLICATIONS 39-27., 127 11/1964 Japan 260/281 OTHER PUBLICATIONS Rice et a1., Jour. Med. Chem. Vol. 11, (Jan 68).

Primary ExaminerDonald G. Daus Assistant Examiner-Ralph D. McCloud Attorney, Agent, or Firm-Browne, Beveridge, DeGrandi & Kline 5 7] ABSTRACT Acrylic fibre-bleaching cation composition of matter in which the cation has the formula:

in which Ris an alkyl radical or a hydroxy or alkoxy substituted alkyl radical, said alkyl having one to four carbon atoms, X is a direct linkage or p-phenylene, B

5 Claims, No Drawings t-NAP MIIZQ CYCLOAMMONIUM-ACRYLIC FIBER COMPOSITIONS This application is a divisional application .of copendingapplication Ser. No. 751,349 filed Aug. 9, 1968, now U.S. Pat. No. 3,649,633.

The present invention concerns new optical bleaching agents, their preparation and their applications.

The agents of this invention are novel cationic organic compounds which can be used as fluorescent brightening agents for fibres based on acrylonitrile polymers or copolymers and they are derivatives of naphthalic anhydride corresponding to the general formula:

N-BEB in whichR represents an alkyl radical, B represents a cycloammonium group and A represents a colourless monovalent anion.

The radical R is preferably an alkyl radical containing from one to four carbon atoms for example, methyl, ethyl, propyl or isopropyl groups. These radicals may be substituted by at least one non-chromophore and non-anionic substituent such as for example a hydroxy or alkoxy group.

By cycloammonium group is meant a monoor poly-cyclic heterocyclic group containing one or more hetero atoms, the hetero atom or one of the hetero atoms being a quaternary nitrogen atom. Examples of such groups are pyridinium, imidazolium, benzimidazolium, pyrazolium, pyrazolinium, triazolium, thiazolium, benzothiazolium, oxazolium, isoxazolium, benzo-oxazolium, oxadiazolium, thiadiazolium, quinolium and indazolium rings. These rings may be substituted by at least one non-chromophore and nonanionic substituent. They may be attached through a carbon atom to naphthalimido group either by a direct linkage orby a p-phenylene radical.

The cationic organic compounds of the invention are salts which are soluble in water, and their aqueous solutions show an intense green-blue fluorescence. They have a good affinity for synthetic fibres based on acrylonitrile polymers or copolymers, with which they form true compounds, the cations being attached at the negative positions of the fibre. They impart to the acrylic fibres-a remarkable effect of whiteness which persists on repeated washing and is stable to light and steaming and fast to chlorine.

Alkoxylated derivatives of naphthalimides are already known. Anselm and Zuckmeyer (Ber., 1899, 32, p. 3,291) have prepared 4-methoxy-N- methylnaphthalimide. Similarly French Pat. Nos. 1,322,849 and 1,344,883 and U.S. Pat. No. 3,310,564 describe 4-alkoxy-naphthalimides in which the nitrogen atom is substituted by hydrocarbon radicals. These substances are insoluble in water, which makes their application complicated owing to the fact that they have to be very finely dispersed. Those which have a fluorescent brightening action on acrylic fibres owe it to absorption by the fibre, but not to a true chemical combination with the latter.

The compounds of formula (I) can be prepared for example by reacting an alkylating agent of formula A- alkyl wherein A has the meaning given above, for example, an alkyl halide, sulphate or sulphonate, with a compound of the general formula:

in which R has the meaning given above and B repre sents a heterocyclic, monoor poly-cyclic group containing one or more atoms of nitrogen or one or more hetero-atoms one of which is a nitrogen atom, possibly in the presence of a solvent such as for example an aromatic hydrocarbon or a chlorinated derivative thereof, an alcohol or dimethyl formamide. The preferred alkylating agent is an alkyl sulphate such as, for example, methyl sulphate.

The compounds of formula (11) may be obtained for example by any of several known processes, for example by the condensation of a 4-alkoxy-naphthalic anhydride, and especially 4-methoxy-naphthalic anhydride (C. 1926, 11, p.281? J. Chem. Soc. 1939, p.792), with a heterocyclic primary amine of the formula:

in which E has the meaning given above.

It is also possible to prepare the compounds of formula II from 4-bromo-naphthalimides of the formula:

temperature between C. and 200 c. Ethylene glyco] and diethylene glycol, which can be used in a very wide range of temperature, are particularly suitable solvents. The bromonaphthalimides of formula (IV) can then be converted into alkoxynaphthalimides of the formula (II), owing to the mobility of the bromine atom. This property is pointed out by Graebe (Liebigs Ann., 327, p. 87) and by Bradley and Pexton (J. Chem. Soc., 1954, p.4434). For this conversion the bromonaphthalimides of formula (IV) may be treated in an excess of alcohol ROH at the boiling point or under pressure with an alkali metal alcoholate of formula ROMe, in which R has the meaning given above and Me is an alkali metal, preferably sodium.

The quaternary salts of formula (I) are very soluble in water, and their solutions are extremely fluorescent in daylight and still more under the influence of ultraviolet rays. They may be applied to fibres based on acrylonitrile polymers or copolymers such as those sold under the trade names Orlon," Courtelle, Crylor, or Dralon, either by dyeing in a bath having a pH of from 4 to 7 or by any other process such as for example thermo-flxation or incorporation in the mass during spinning. A very small amount of the product, of the order of 0.1 to 0.4 percent is sufficient to obtain an excellent whitening effect.

The naphthalimides of the formulae (II) or (IV) are new compounds but for the most part they have weak fluorescent properties and an affinity for fibres which is too small to have an optical bleaching effect of any interest. In these circumstances it was unexpected that the conversion of the naphthalimides of formula (II) into their quaternary derivatives would considerably increase the fluorescence of these compounds.

The following Examples 1 to 61 illustrate the preparation of these intermediate products. Examples 62 to 84 illustrate the preparation of cycloammonium derivatives of naphthalimides according to theinvention. Examples 85 and 86 illustrate the use of the cycloammonium derivatives on acrylic flbres. These Examples are purely illustrative and the parts given are parts -pyrazolyl)-naphthalimide, weight.

Naphthalimides of formula (IV) EXAMPLE 1 14 parts of 4-bromo-naphthalic anhydride are condensed with 5.2 parts of 2-aminopyn'dine in 100 parts of ethylene glycol by heating the mixture for 5 hours at l30-l40 C. After cooling, the precipitate is filtered off, washed with water and dried. 17.4 parts of 4- bromo-N-(2-pyridyl)-naphthalimide, melting at 247248 C. are obtained, of the formula:

00 700 i 3 3.. L EXAMPLE 2 melting at 267 C, are obtained. of the formula:

on replacing the 2-aminopyridine in Example I with 5 other heterocyclic amines B'NH and operating in a similar way, the following bromo-naphthalimides are obtained:

Exam B-NH Naphthalimides of formula W M.p. C

ple

3 3-aminopyridine 4-bromo-N-(3-pryridyl) nuphthal- 2l7 imide 4 2-amino-6-methyl- 4-bromoN-(6-methyl2-pyridyl)- 238 pyridien naphthulimide 5 Z-aminothiazole 4-bromo-N-( Z-thiazolyl l-naphth- 298 alimide 6 2-amino-4-methyl- 4-bromo-N-(4-methyl2-thiuzolyl)- 248 thiazole naphthalimide 7 Z-amino-benzo- 4-bromo-N-(Z-benzothiazolyh- 300 thiazole naphthalimide 8 6-amino-2-phenyl- 4-bromo-N(2-phenyl-6'benzo- 308 benzothiazole thiazolyl )-naphthalimide 9 4'-amin0-2-phenyl- 4-bromo-N-[4 (2-benzothiu20lyl)- 326 benzothiazole phenyll-naphthnlimide l0 Z-umino-benzoxazole 4-bromo-N-( Z-benzoxazolyl 285 nuphthalimide ll 5-amino-3-methyl- 4-bromo-N-( 3-methyl-5Jsoxazo- 295 isoxazole lyl)-nuphthulimide l2 6-amino-2 methyl- 4-bromo-N-( 2-methyl-6-quinolyl Z87 quinoline naphthalimide l3 2-aminobenzimid- 4-bromo-N-( Z-benzimiduzolyl 335 azole naphthalimide l4 6-amino-l ,Z-diemth- 4-bromo-N-( l,2diemthyl-6-benz- 325 yl-benzimidazole imidazolyl)-naphthalimide l5 4 '-umino-2-phenyl- 4-bromo-N-l4-( Z-benzimidazolyl 320 benzimidazole phenyll-naphthalimide l6 4'-amino-2-phenyl- 4-bromo-N-[4-( l-methyLZ-benz- 273 l-methyl-benzimidazolyl) phenyll-naphthimidazole alim' e I? fi-umino-indazole 4-bromo-N-(6-induzolyl)'naphlh- 305 mi l 8 -aunino-6-chloro- 4hmmn-N4 (i-chluro-limlamlyl 3 25 indazole nuphthulimide l9 2-amino-5-methyl- 4-bromo-N-( S-methylthio-Z-thiu- 240 thio-thiadiazole diazolyl )-nuphthulimide 4-methoxy-na'phthalimides are obtained, the melting v points of which are given below:

w -'Continued Exam B'-NH Naphthalimides of formula IV M.p. C

3-amino-4-phenyl- 4-brom0-N-(4-phenyl-3-pyrazolyl)- V 298 pyrazole naphthalimide 2l 3-ammo-5-phenyl- 4-brom0-N-(5-phenyl-3-pyrazolyl 286 pyrazole naphthalimide 22 3-ammo-5-methyl-4- 4-bromo-N-(5-methyl-4 phenyl-3- 302 phenyl-pyra2ole pyrazolyU-naphthalimide 23 4-amino-3-methyl-5- 4-bromo-N-( 3 methy|-5-phenyl-4- 254 phenyl-pyrazole pyrazolyli-naphthalimide 24 4 -aminol-phenyl- 4br0mo-N-[4-(3,5-dimethyl-L 245 3.5-dimethylpyraz'olyl)-phenyl]-naphthpyrazole alimide 25 4-amino-l-phenyl- 4-brom0-N-[4-(3,5,5-trimethyl 238 3,5.5trime'thyl- I-A2-pyrazolinyl)-phenyl]- AZ-pyrazoline naphthalimide 26 3-amino-l ,2,4-4H-tri 4-bromo-N-(1,2.4-4l-l-triazol- 350 azole 3-yl)-naphthalimide 27 3-amino-5-phenyl- 4-bromo-N-( 5-phenyl-l ,2,4-4l-l- 345 1,2,4-4H-triatriazol-3-yl-naphthalimide zole 28 4-aminol ,2,4-4H- 4-bromo-N-(1.2,4-4H-triaz0l- 350 triazole 4-yl)-naphthalimide 29 4-amino-3- henyl- 4-bromo-N-[4(5-methyl-l,2,4- 300 5methyl- ,2,4- 4H-triazol-3-yl)-phenyl]- 4H.-triaz0le naphthalimide Naphthalimides of formula (II) Ommued- Example Initial 4-br0mo-haphthalimide M.p. of the EXAMPLE 3O 4-methoxy derivi ative in "C 4 parts of sodium are dissolved in 250 parts by voln ume of methyl alcohol in an apparatus provided witha 16 4 stirrer aiid a reflux condenser. Then 14.12 parts of 4- 1 3 3 bromo-N-(2-pyridyl)-naphthalimide are added and the 42 8: 19 decomposition mixture is heated under reflux for 3 hours. The reaction 43 2 mixture thickens and becomes a pale yellow colour. 44 21 292 4 t 45 do. 22 290 After cooling, the precipitate is filtered off, taken up in 46 23 250 dilute acetic acid, filtered and washed with water, then 47 do. 24 247 with alcohol. After drying, 11.3 parts of 4-methoxy-N- 2g 3gg-g (2-pyridyl)-naphthalimide ofmeltiiig point 240 C. are 50 5 350 obtained. On rec'rystallising from a mixture of alcohol 51 do. 28 345 and dimetliyl formamide, the product forms long y'el- 52 29 305 low needles melting at 242 C.

By application of the same process to the 4-bromonaphthalimides of Examples 2 to 29, the corresponding EXAMPLE 53 A mixture of 1 parts of 4-met hoxy-naphthalic anhydride with 4.7 parts of Z-aminopyridirie and 100 Example initial4-bromo-naphthalimide M.p.ofthe Parts of y n "g yw is heated for a -"j':} y g l-160 C. with stirring. After cooling, filtering off a We m the precipitate, washing with alcoholand drying, 13 31 Example 2 255 parts of a product similar to that from Example 30 are 3; a: 2 532 5., obtained- 34 5 250 On operating as in the preceding Example, but re- 35 6 235 placing the Z-aminOpyridine by equivalent quantities of g3 g3: 12 538 the following heterocyclic amines the corresponding 38 do, 15 309 4-methoxy-naphthalimides are obtained:

Example B-NH Naphthalimides of formula II M.p.C

54 Z-amino-benzothia- 4-methoxy-N-)Z-benzothiazo- 220 zole lyl)-naphthalimide S5 6-amino-2-phenyl- 4-methoxy-N-(2-phenyl-6- 350 benzothiazole benzothiazolyli-naphthalimide 56 Z-amino-benzoxazole 4-methoxy-N-(2-henzoxazolyl)- 320 naphthalimide 57 6-amino-2-phenyl- 4-methoxy-N-(2-phenyl-6- 336 benzoxazole benzoxazoIyU-naphthalimide 58 6-amino-2-methyl- 4-methoxy-N42-methyl-6- 25S quinoline quinolyl)-naphthalimide 59 2-amino-4-methyl- 4-methoxy'N-(4-methyl-2- 262 quinoline quinolyl)-nuphthalimide EXAMPLE 60 EXAMPLE 61 On replacing the 4-bromo-N-( 2-pyridyl naphthalimide in the preceding Example by 13.7 parts of 4-bromo-N-( 1 ,2,4-4l-l-triazol-3-yl )-naphthalimide, 4-ethoxy-N-( l,2,4-4l-l-triazol-3yl)-naphthalimide of melting point 338 C. is obtained.

Naphthalimides of formula (I) EXAMPLE 62 parts of methyl sulphate are introduced into an apparatus provided with a stirrer and a thermometer and are heated to 100 C. and 10 parts of 4-methoxy-N- (2-pyridyl)-naphthalimide are then gradually introduced. The temperature of the mixture is raised to 130C. and this temperature is maintained for about an hour, until a sample taken is completely soluble in water. The product is allowed to cool, diluted with 50 parts of water and left with stirring to decompose the excess methyl sulphate. It is then boiled with a little decolorising charcoal and filtered. After cooling, 10 parts of sodium chloride are added to the filtrate, then a dilute solution of zinc chloride, until precipitation is complete. After filtering and drying the precipitate, 12 parts of the chlorozincate of 4-methoxy-2- naphthalimidol-methyl-pyridinium monohydrate are obtained. After recrystallising from water, analysis gives the following figures:

Calculated for C H N O CI V: ZnCl H 0 C 51.8 H 3.86 N 6.36 CI 16.1 Found 51.96 3.90 6.70 16.7

This product is in the form of a light beige crystalline powder, and is very soluble in water. Its dilute aqueous solutions show an intense blue fluorescence.

EXAMPLE 63 the mixture is heated at 130 C. until a sample is soluble in water. After cooling, 50 parts of water are added, the product is boiled with a little decolorising charcoal and filtered. Sodium chloride is added to the filtrate. A light yellow crystalline product is precipitated. 5 parts of 4'- methoxy-2-naphthalimidol ,3-dimethylbenzimidazolium chloride are thus obtained. After recrystallising from water, analysis gives the following resu ts:

Calculalted for C H N O cl, H 0 71: C

Found This compound gives extremely fluorescent aqueous solutions.

EXAMPLE 64 8 parts of 4-methoxy-N-[4-(3,5-dimethyl-l- .pyrazolyl)-phenyl]-naphthalimide (Example 47) are heated under reflux in parts by volume of chlorobenzene and 5 parts of methyl sulphate are introduced in a period of an hour. The mixture is boiled for 2 hours and the solvent is removed by steam distillation. The solution is treated with carbon black, filtered, then cooled. The chlorozincate of 4-methoxy-4'- naphthalimido-1-phenyl-2,3,S-trimethyl-pyrazolium is precipitated by the addition of salt and a solution of zinc chloride.

EXAMPLE 65 3 parts of 4-methoxy-N-( l ,2,4-4H-triazol-4-yl)- naphthalimide from Example 51 are gradually introduced into 5 parts of ethyl sulphate heated to C. This temperature is maintained until a sample is soluble in water. The mass is dissolved in water. The solution is boiled with'decolorising charcoal, filtered and sodium chloride and zinc chloride are added to the cooled solution. 4'-methoxy-4-naphthalimido-l-ethyl- (or 2-ethyl)-triazolium chlorozincate is thus obtained in the form of a light yellow powder which is soluble in water with an intense blue fluorescence.

EXAMPLES 66 to 84 On operating in a similar way according to one of the processes described in Examples 62, 63 and 64 the salts (chlorozincate or methyl sulphate) of other cycloammonium derivatives of formula (1) are obtained from 4-alkoxy-naphthalimides of formula (11) and previously described.

methyl-benzimidazolium (chlorozincate) Continued Exam- Naphthalple imide of formula ll Naphthalimide of formula I of Example:

I ,3-dimethyl-benzimidazolium (chlorozincate) indazolium (chlorozincate) 43 methoxy-3-naphthalimido-4-phenylmethoxy-6-naphthalimido-l ,2-dimethylinelhoxy-4' naphthalimido-Zphenyl 1,2-dimethyl-pyrazolium (methyl sulphate) 1,2dimethyl-pyrazolium (chlorozincate) methoxy-3-naphthalimio-4-phenyll,2,S-trimethyl-pyrazolium (methyl sulphate) 2,4,5-trimethyl-triazolium (chlorozincate) methoxy-3-naphthalimido-S-phenylmethoxy-4naphthalimido-S-phenylmethoxy-4-naphthalimidol -phenyl- 2,3,S-trimethyl-pyrazolium (chloromethoxy-3naphthaIimido-S-phenylmethoxy-4 -naphthalimido-3-phenylmethoxy-3-naphthalimido-2.4-dimethylmethoxoyA-naphthalimidol ,2,3,5-tetramethyl- EXAMPLE EXAMPLE 86 The operation is carried out exactly under the conditions described in Example 85, but 5 parts of sodium chlorite have been previously added to the bath. The optical bleaching effect observed is still more intense.

We claim:

1. A composition of matter consisting of cations and an acrylic fiber having negative positions, said cations being attached at the negative positions of said fiber, in which' the cations have the formula:

in which R is alkyl or monohydroxy or monoalkoxy substituted alkyls oralkoxy group, said alkyl having one to four carbon atoms, X is a carbon-nitrogen linkage or p-phenylene, B is an N"- (lower alkyl) cycloammonium said cycloammonium being a benzimidazolium, pyrazolium, triazolium or thiazolium group, wherein lower alkyl is methyl or ethyl, said cycloammonium group attached to X through a carbon atom, B being unsubstituted on the remaining carbon atoms or substituted on said carbon atoms by up to four substituents selected from the group consisting of chlorine, methyl, ethyl, phenyl or methylthio.

2. composition of matter as claimed in claim 1 in which B is benzimidazolium.

3. composition of matter as claimed in claim 1 in which B is pyrazolium.

4. Composition of matter as claimed in claim 1 in which B is triazolium.

5. Composition of matter as claimed in claim 1 in which B is thiazolium. 

1. A COMPOSITION OF MATTER CONSISTING OF CATIONS AND AN ACRYLIC FIBER HAVING NEGATIVE POSITIONS, SAID CATIONS BEING ATTACHED AT THE NEGATIVE POSITIONS OF SAID FIBER, IN WHICH THE CATIONS HAVE THE FORMULA:
 2. composition of matter as claimed in claim 1 in which B is benzimidazolium.
 3. composition of matter as claimed in claim 1 in which B is pyrazolium.
 4. Composition of matter as claimed in claim 1 in which B is triazolium.
 5. Composition of matter as claimed in claim 1 in which B is thiazolium. 